Polymer 80 (2015) 64e66

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Polymer
journal homepage: www.elsevier.com/locate/polymer

Short communication

Toward the (nearly) complete elimination of solvent waste in Ring

Opening Metathesis Polymerization (ROMP) reactions
Manasa Shetty, Venkata A. Kothapalli, Christopher E. Hobbs*
Department of Chemistry, Texas A&M University-Kingsville, Kingsville, TX 78363, USA

a r t i c l e i n f o a b s t r a c t

Article history: This short communication describes current efforts geared toward the development of solvent-free, Ring
Received 21 August 2015 Opening Metathesis Polymerization (ROMP) processes. It has been found that the preparation of homo
Received in revised form and copolymers can be accomplished under solvent-free ROMP reaction conditions using both liquid and
15 October 2015
solid monomers under air. Typical reactions are operationally simple and can be run under air and the
Accepted 19 October 2015
Available online 22 October 2015
polymer products can be isolated using minimal amounts of organic solvents.
© 2015 Elsevier Ltd. All rights reserved.
Keywords:
Metathesis
Green chemistry
ROMP

1. Introduction amounts of organic solvents that subsequently need to be properly

The development of controlled polymerization techniques has
revolutionized the field of polymer science. Such methods allow
chemists to incorporate a seemingly infinite combination of func-
tionality into designer macromolecules that can be used for
numerous applications. These polymerization techniques include
living radical polymerizations, such as ATRP [1] and RAFT [2].
However, one of the most widely used techniques is the Ring
Opening Metathesis Polymerization (ROMP) [3], usually facilitated
by the highly functional group tolerant Grubbs-type initiators, such
as 1 and 2 (Fig. 1).
Various highly strained cyclic olefins (such as norbornene,
cyclooctene and 1,5-cyclooctadiene derivatives) can be polymer-
ized using ROMP reactions that are typically carried out in organic
solvents such as DCM or THF. The amount of solvent waste gener-
ated from these reactions on academic-laboratory scale does not
represent an insurmountable obstacle, but can be problematic on
large-scale processes. Furthermore, even if these reactions are run
at higher concentrations with very small amounts of solvent, the
product polymers are often isolated after multiple solvent extrac-
tions using excess amounts of a “poor” solvent. This allows for the
isolation of product as a solid while separating it from much of the
Ru contamination. However, this process can require copious
* Corresponding author.
E-mail address: christopher.hobbs@tamuk.edu (C.E. Hobbs).
disposed of. Additionally, these reactions are typically carried out
under careful extrusion of air using sophisticated glassware,
equipment, and degassed solvents. In the interest of Green chem-
istry, many research groups have developed methods for the
removal of potentially toxic and environmentally detrimental Ru-
species as well as exploring methods that decrease the amount of
organic solvent waste generated (i.e. alternative solvents, polymer
supported catalysts) [4e7].
These systems, however, often require specially designed cata-
lysts or monomers. The design of robust, operationally simple,
“open-flask” and solvent-free processes is ideal. To realize this goal,
Cazin and coworkers [8] have shown that Ring Closing Metathesis
(RCM) reactions can be accomplished using low amounts of catalyst
in the open air. Also, during the course of our study, Fris
ci
c [9] and
coworkers described an exquisite system that relied on mechanical
force to facilitate RCM and Cross Metathesis (CM) reactions, facili-
tated by commercially available catalysts in the absence of (or very
little) organic solvents. While studying new, greener polymer
functionalizations [10,11], we have found that solvent-free ROMP
reactions can be successfully carried out under air in a matter of
minutes. We report our initial results as proof of principle of the
utility of this process toward the polymerization and copolymeri-
zation of a few ROMP monomers.
Solvent-free reaction conditions are very common for acyclic
diene metathesis (ADMET) [12] polymerization and have even been
described in ring closing metathesis (RCM) [13] reactions. Although
the utilization of neat reaction conditions for ROMP reactions is not

http://dx.doi.org/10.1016/j.polymer.2015.10.036
0032-3861/© 2015 Elsevier Ltd. All rights reserved.
 M. Shetty et al. / Polymer 80 (2015) 64e66
Fig. 1. Examples of Grubbs-type initiators for olefin metathesis.
Scheme 1. Neat polymerization of 3 using 2 as initiator.
a novel idea, many of the systems described rely on sophisticated
equipment (Schlenk lines, glove box, etc.) and wasteful solvent
precipitations for product isolation [14e16].
2. Results and discussion
Our initial attempts were carried out using commercially
available HoveydaeGrubbs 2nd Generation initiator 2 in neat 1,5-
cyclooctadiene 3 (Scheme 1). 3 was placed in a vial and, while
vigorously stirring, 2 was quickly added under air. Within 20 s, the
reaction mixture became solid and noticeably warm. However, the
resulting material was only sparingly soluble in common organic
solvents (such as DCM or THF), possibly due to the formation of
extremely high molecular weight materials. Because of this, its
characterization was rendered difficult.
To circumvent this issue, we attempted this process using 1, a
faster initiating initiator that was readily available to our laboratory
as opposed to the even-faster initiating pyridine complexes [17];
these species would have required preparation from 1 using excess
amounts of toxic pyridine. Advantageously we found that 1 facili-
tated the solvent-free, homopolymerization of 3 in approximately
2 min in an open flask (Fig. 2a). After sitting for 10 min, we planned
a..
1 (5 mol%)
ca. 2 min.
Fig. 2. Photographs of (a.) 3 before and after the addition of 1 and (b.) partial 1H NMR spectra of 3 and the resulting polymer.
Scheme 2. Homopolymerizations of 3 and 4 using initiator 1.
65
on working up the reaction by adding ethyl vinyl ether and THF
followed by precipitation into methanol. But, to our surprise, this
solid reaction mixture was soluble in 2 mL of ethyl vinyl ether.
Beneficially, a solvent precipitation (to remove initiator) could be
avoided, as the resulting viscous solution could be passed through a
short plug of basic alumina. Fresh THF (no more than 1 mL) was
then passed through this plug. Removal of this solvent provided the
polymeric product as an off white solid. Analysis by 1H NMR
revealed no 3 remaining in solution (Fig. 2b). Although not
completely solvent-free, this represents an improvement over
typical ROMP procedures that can often call for air/moisture free
apparatus as well as copious amounts of organic solvents.
Pleased with this result, we next set out to determine whether
this procedure was amenable to other typical ROMP monomers
readily available. To our delight, subjecting mixture of endo-and
exo-methyl 5-norbornene-2-carboxylate (4) to the same reaction
conditions produced target polymer in approximately 2 min
(Scheme 2).
It turned out that these polymerizations could be performed
using lower amounts of initiator. Addition of 1 mol % 1 to 3 or 4 led
to polymerization in a matter of minutes to provide homopolymers
in good yield (Table 1, entries 1 and 2). We next set out to apply this
toward the preparation of random copolymers. This turned out to
be possible. Addition of 1 mol % 1 to mixtures of comonomers led to
the formation of various copolymers in good yield (Table 1 and
Scheme 3). Even the less strained cyclopentene 5 could be incor-
porated into copolymers. Gratifyingly, this procedure could also be
used to prepare copolymers of norbornene 6, which is a solid at
room temperature, but is soluble in 3, 4, and 5. Dissolving 6 in
comonomers 3, 4, or 5, followed by addition of initiator 1 led to
complete conversion (1H NMR analysis after quenching revealed no
remaining monomer) in a matter of a couple of minutes (Table 1,
entries 4e6). Addition of ethyl vinyl ether to these mixtures led to a
viscous solution that was then passed through basic alumina.
Although conversions for all reactions appeared to be quantitative,
the isolated yields were lower possibly due to residual polymer
remaining on the alumina. Regardless, all polymers were isolated in
good yield. However, further analysis by GPC, in most cases,
revealed large deviations of Mn from predicted values. Molecular
weight distributions were shown to be mostly monomodal, but
broad, indicating that these polymerizations were not well
controlled (Table 1 and SI).
b.
n
6 4 2 ppm
66 M. Shetty et al. / Polymer 80 (2015) 64e66

Table 1
Polymerizations of 3, 4, 5 and 6 using initiator 1 at lower initiator loading.

entrya,b Mon. Mon. Polymer Yieldc (%) Mn (pred.) (Da) Mn (Da)d Mw/Mn d

1 3 e 7 98 10,818 19,450 3.01

2 4 e 8 81 15,219 42,100 3.64
3 4 9 88 12,116 19,200 1.87

5
4 3 10 76 11,128 20,500 2.47

6
5 4 6 11 95 13,549 44,800 2.32
6 5 6 12 88 8924 9608 2.27
a
Conditions: [monomer]:[initiator] (100:1), ethyl vinyl ether (2 mL), followed by passing through basic alumina.
b
Conditions: [monomer]:[monomer]:[initiator] (55:55:1), ethyl vinyl ether (2 mL), followed by passing through basic alumina.
c
Isolated yield.
d
Determined by GPC.

Scheme 3. Structures of polymer products 7e12.

3. Conclusion Appendix A. Supplementary data

In conclusion, we have described a general method that allows Supplementary data related to this article can be found at http://
for ROMP reactions to be performed in an operationally simple dx.doi.org/10.1016/j.polymer.2015.10.036.
process. These reactions take place under neat conditions, in open
flasks in a matter of minutes. Although not completely solvent free, References
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